CN101851331A - Soluble high-performance polyimide and preparation method thereof - Google Patents
Soluble high-performance polyimide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses soluble high-performance polyimide and a preparation method thereof. The structure of the polyimide is shown as a formula (I), wherein groups'-A-' in each unit in the formula (I) are groups shown by a formula (II) or (III) independently, and the groups shown by the formulas (II) and (III) exist in the structure of the polyimide simultaneously. The preparation method comprises the following steps of: dissolving organic dianhydride pyromellitic anhydride and an organic diamine monomer into a solvent with a high boiling point, stirring the mixture mechanically under the protection of inert gases, heating to the temperature of between 180 and 220 DEG C for polymerization reaction for 3 to 7 hours, and performing aftertreatment on a reaction liquid to prepare the polyimide, wherein the organic diamine is a mixture of 4,4'-diaminodiphenyl sulfone and 4,4'-bi(3-amino phenoxybenzene) sulphone in a molar ratio of 1:0.1-10. The polyimide has the advantages of excellent thermal performance, machining performance and dissolution performance, convenient operation in the preparation process, simple process, low cost and easy industrial production.
Description
(1) technical field
The present invention relates to a kind of soluble high-performance polyimide and preparation method thereof.
(2) background technology
The polyimide molding material is the macromolecular material that a class has significant application value, is widely used in fields such as space flight, aviation, electronics, electric, mechanical, automobile.Such material not only has the favorable mechanical performance, and has good thermotolerance, chemicals-resistant corrodibility and insulating property.Simultaneously compound with other materials, also can be used for self-lubricating, sealing, thrust washer, bullet train brake lining etc.
But, use pyromellitic acid anhydride (PMDA) synthetic polyimide owing to rigidity in the PMDA molecular chain is excessive, the polyimide that obtains is generally insoluble, molten, very poor in processability.In order to improve the processing characteristics of polyimide, synthesized different dianhydride and the diamine monomer of hundreds of structure, relation to polyimide structures and performance has been carried out detailed research, and developed the listing of tens kinds of thermoplastic polyimide commodity, the Ultem that puts on market of nineteen eighty-two GE company for example, the Aurum and the back of Mitsui east pressure company are developed the better SuperAurum of performance again, also have Changchun applied chemistry institute of China Chinese Academy of Sciences and Shanghai synthetic resins two families, YHPI of Sheng Chenging and YS20 respectively.
The melt-processable of polyimide molding powder and the chemical structure of its polymkeric substance are closely related.Because it is a lot of to influence the factor of polyimide melt-processable, wherein topmost influence factor comprises: the chemical structure of (1) main polymer chain; (2) chemical structure of polymer lateral chain; (3) interaction between the main polymer chain; (4) crystal property of polymkeric substance etc.The main chain of polymkeric substance and side chain chemical structure mainly are to be subjected to the chemical structure of polymer monomer and substituent influence of being with thereof, and interaction between the main polymer chain and crystal property mainly are to be subjected to contained bridged bond in the backbone structure, as-O-,-CO-etc. and side-chain structure in the substituting group Effect on Performance, comprise the position isomerism of flexible group, the size of side group etc.
(3) summary of the invention
The primary technical problem that the present invention will solve provides a kind of polyimide with good thermal characteristics, processing characteristics and solubility property.
The structure of polyimide of the present invention is suc as formula shown in (I), and expression is made up of n unit, and n is a natural number:
Group " A-" in each unit in its Chinese style (I) independently is selected from the group shown in formula (II) or the formula (III):
And have the group shown in formula (II) and the formula (III) in the formula (I) simultaneously, the unit number that contains the group shown in the formula (II) is any ratio with the ratio that contains the unit number of the group shown in the formula (III).The described unit number that contains the group shown in the formula (II) of the concrete recommendation of the present invention is 1: 0.1～10 with the ratio that contains the unit number of the group shown in the formula (III), more preferably 1: 1～4.
The limiting viscosity of polyimide of the present invention is at 0.4～0.7dL/g, and second-order transition temperature is more than 270 ℃, tensile strength 70-110Mpa, and flexural strength 100-150Mpa, heat-drawn wire dissolves in NMP (N-Methyl pyrrolidone) more than 260 ℃.Limiting viscosity among the present invention under 30 ℃, is that solvent records with NMP all.
Second technical problem that the present invention will solve be to provide a kind of easy to operate, technology is simple, with low cost, the preparation method that is easy to industrialized polyimide.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of preparation method of polyimide, specific as follows: that organic dianhydride and organic diamine monomer are dissolved in the high boiling solvent, mechanical stirring under protection of inert gas, be heated to 180～220 ℃ of polyreactions 3～7 hours, and again reaction solution poured into precipitation, filtration, washing, drying obtained described polyimide in methyl alcohol, acetone, ethanol or the water; Described organic dianhydride is that structure is suc as formula the pyromellitic dianhydride shown in (IV), described organic diamine be structure shown in formula V 4,4 '-diaminodiphenylsulfone(DDS) and structure are suc as formula 4 shown in (VI), than 1: 0.1～10 mixing, described high boiling solvent is the wherein a kind of of meta-cresol, NMP, cresols, para-chlorophenol or two or more mixed solvent arbitrarily to 4 '-two (3-amino-benzene oxygen benzene) sulfone with amount of substance;
Organic diamine of the present invention is generally 0.9～1.1: 1.0 with the amount of substance ratio of organic dianhydride, preferred reaction with same mole, the polyimide limiting viscosity maximum that obtain this moment.
Of the present invention 4,4 '-two (3-amino-benzene oxygen benzene) sulfone and 4,4 '-diaminodiphenylsulfone(DDS) feed intake the amount of substance ratio can be any, those skilled in the art can adjust and control according to actual needs, thereby obtain the polyimide series of products of different temperature resistant grades, mechanical property.The present invention recommends described 4,4 '-two (3-amino-benzene oxygen benzene) sulfone and 4, and the amount of substance ratio that feeds intake of 4 '-diaminodiphenylsulfone(DDS) is 0.1～10: 1, and preferred 1～4: 1, more preferably 3～4: 1.
The present invention recommends employed organic dianhydride and organic diamine total mass to account for the 10-45% of reaction mass total mass.Described " reaction mass " is made up of organic dianhydride, organic diamine, high boiling solvent.
The mixed solvent of preferred meta-cresol of high boiling solvent of the present invention and NMP, the volume ratio of meta-cresol and NMP is 0.2～5: 1 in the mixed solvent of preferred meta-cresol and NMP, preferred 0.5～2: 1.
Preparation process of the present invention is recommended under the nitrogen protection carries out.
The present invention preferably constantly steams the water of generation in polymerization process, carry out to the direction that forms polymkeric substance to impel polyreaction, obtains the high-molecular weight polyimide resin.
Controlled polymerization temperature of the present invention is at 180～220 ℃, and under this polymerization temperature, polyimide is dissolved in reaction system fully in the building-up process, and therefore, the polyimide that obtains not only molecular weight can suitably increase and narrowly distributing.Further, in preparation process, preferably be heated to 200～205 ℃ of reactions 4～5 hours.
The polyimide that the present invention makes is a powdery product, can be used for compression molding, and product can be applicable to the sealing member, bearing, gear in high temperature resistant field etc.
Compared with prior art, beneficial effect of the present invention is embodied in:
A) polyimide of the present invention has the high thermal resistance of infusibility polyimide and workability and the good mechanical performance and the solubility property of plasticity-polyimide simultaneously.Relative infusible polyimide, the polyimide of present method preparation can adopt mold pressing or injection moulding process to make plastics or section bar, greatly reduces difficulty of processing.With respect to thermoplastic polyimide, polyimide thermotolerance of the present invention improves greatly, and second-order transition temperature reaches 280 ℃.Thereby the ratio that simultaneously can be as required be mixed with two kinds of components in the organic diamines by adjusting obtains the polyimide series of products of different temperature resistant grades, mechanical property.
B) preparation method of the present invention's employing uses cheaper pyromellitic acid anhydride to be raw material, greatly reduces cost.Simultaneously, adopt single step reaction, have easy to operate, technology simple, be easy to characteristics such as industrialization.
(4) specific embodiments
With specific embodiment technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto:
Embodiment 1
In the 250ml four-hole boiling flask, add 3.24g 4 successively, 4 '-two (3-amino-benzene oxygen benzene) sulfone (7.5mmol), 0.62g 4,4 '-diaminodiphenylsulfone(DDS) (2.5mmol), 2.18g pyromellitic acid dianhydride (10mmol), the 19g meta-cresol, 19g NMP, logical nitrogen adds the water that a constant pressure funnel (interior dress molecular sieve) replaces water trap to remove generating in the dereaction, heated and stirred before the return line, be warming up to 60 ℃, reactant dissolves fully, is the brown clear solution, continues to be warming up to 200 ℃, in 200 ℃ of reaction 5h, in the process of cooling solution too thickness can add small amount of methanol dilution, when being cooled to 60 ℃, reaction solution being poured in the 150ml methyl alcohol precipitates, filter, washing, drying gets buff powder 5.6g, yield 98.6%, limiting viscosity is 0.55dL/g, and Tg is 288.4 ℃, tensile strength 96Mpa, flexural strength 140Mpa, 275 ℃ of heat-drawn wires.
Embodiment 2
In the 250ml four-hole boiling flask, add 2.88g 4 successively, 4 '-two (3-amino-benzene oxygen benzene) sulfone (6.7mmol), 0.82g 4,4 '-diaminodiphenylsulfone(DDS) (3.3mmol), 2.18g pyromellitic acid dianhydride (10mmol), the 21g meta-cresol, 21g NMP, logical nitrogen adds the water that a constant pressure funnel (interior dress molecular sieve) replaces water trap to remove generating in the dereaction, heated and stirred before the return line, be warming up to 60 ℃, reactant dissolves fully, is the brown clear solution, continues to be warming up to 200 ℃, in 200 ℃ of reaction 5h, in the process of cooling solution too thickness can add small amount of methanol dilution, when being cooled to 60 ℃, reaction solution being poured in the 150ml methyl alcohol precipitates, filter, washing, drying gets buff powder 4.91g, yield 89.0%, limiting viscosity is 0.5dL/g, and Tg is 283.1 ℃, tensile strength 91Mpa, flexural strength 132Mpa, 269 ℃ of heat-drawn wires.
Embodiment 3
In the 250ml four-hole boiling flask, add 3.46g 4 successively, 4 '-two (3-amino-benzene oxygen benzene) sulfone (8mmol), 0.49g 4,4 '-diaminodiphenylsulfone(DDS) (2mmol), 2.18g pyromellitic acid dianhydride (10mmol), the 20g meta-cresol, 20g NMP, logical nitrogen adds the water that a constant pressure funnel (interior dress molecular sieve) replaces water trap to remove generating in the dereaction before the return line, heated and stirred, be warming up to 60 ℃, reactant dissolves fully, is the brown clear solution, continue to be warming up to 200 ℃, reaction solution is a brown solution, in 200 ℃ of reaction 5h, in the process of cooling solution too thickness can add small amount of methanol dilution, when being cooled to 60 ℃, reaction solution poured in the 150ml methyl alcohol precipitate, filter, washing, dry, get buff powder 5.65g, yield 98.0%, limiting viscosity is 0.64dL/g, Tg is 270.1 ℃, tensile strength 91Mpa, flexural strength 139Mpa, 260 ℃ of heat-drawn wires.
Embodiment 4
In the 250ml four-hole boiling flask, add 2.16g 4 successively, 4 '-two (3-amino-benzene oxygen benzene) sulfone (5mmol), 1.24g 4,4 '-diaminodiphenylsulfone(DDS) (5mmol), 2.18g pyromellitic acid dianhydride (10mmol), the 22g meta-cresol, 22g NMP, logical nitrogen adds the water that a constant pressure funnel (interior dress molecular sieve) replaces water trap to remove generating in the dereaction before the return line, heated and stirred, be warming up to 60 ℃, reactant dissolves fully, is the brown clear solution, continue to be warming up to 200 ℃, reaction solution is a brown solution, in 200 ℃ of reaction 5h, in the process of cooling solution too thickness can add small amount of methanol dilution, when being cooled to 60 ℃, reaction solution poured in the 150ml methyl alcohol precipitate, filter, washing, dry, get buff powder 4.99g, yield 95.6%, limiting viscosity is 0.51dL/g, Tg is 274.1 ℃, tensile strength 89Mpa, flexural strength 128Mpa, 261 ℃ of heat-drawn wires.
Embodiment 5
In the 250ml four-hole boiling flask, add 3.24g 4 successively, 4 '-two (3-amino-benzene oxygen benzene) sulfone (7.5mmol), 0.62g 4,4 '-diaminodiphenylsulfone(DDS) (2.5mmol), 2.18g pyromellitic acid dianhydride (10mmol), the 16g meta-cresol, 16g NMP, logical nitrogen adds the water that a constant pressure funnel (interior dress molecular sieve) replaces water trap to remove generating in the dereaction before the return line, heated and stirred, be warming up to 60 ℃, reactant dissolves fully, is the brown clear solution, continue to be warming up to 180 ℃, reaction solution is a brown solution, in 180 ℃ of reaction 7h, in the process of cooling solution too thickness can add small amount of methanol dilution, when being cooled to 60 ℃, reaction solution poured in the 150ml methyl alcohol precipitate, filter, washing, dry, get buff powder 5.5g, yield 96.8%, limiting viscosity is 0.48dL/g, Tg is 280.1 ℃, tensile strength 102Mpa, flexural strength 138Mpa, 269 ℃ of heat-drawn wires.
Embodiment 6
In the 250ml four-hole boiling flask, add 3.24g4 successively, 4 '-two (3-amino-benzene oxygen benzene) sulfone (7.5mmol), 0.62g 4,4 '-diaminodiphenylsulfone(DDS) (2.5mmol), 2.18g pyromellitic acid dianhydride (10mmol), the 20g meta-cresol, 20g NMP, logical nitrogen adds the water that a constant pressure funnel (interior dress molecular sieve) replaces water trap to remove generating in the dereaction before the return line, heated and stirred, be warming up to 60 ℃, reactant dissolves fully, is the brown clear solution, continue to be warming up to 220 ℃, reaction solution is a brown solution, in 220 ℃ of reaction 3h, in the process of cooling solution too thickness can add small amount of methanol dilution, when being cooled to 60 ℃, reaction solution poured in the 150ml methyl alcohol precipitate, filter, washing, dry, get buff powder 5.46g, limiting viscosity is 0.53dL/g, yield 96.1%, Tg is 286 ℃, tensile strength 95Mpa, flexural strength 119Mpa, 271 ℃ of heat-drawn wires.
Embodiment 7
In the 250ml four-hole boiling flask, add 3.24g4 successively, 4 '-two (3-amino-benzene oxygen benzene) sulfone (7.5mmol), 0.62g 4,4 '-diaminodiphenylsulfone(DDS) (2.5mmol), 2.40g pyromellitic acid dianhydride (11mmol), the 20g meta-cresol, 20g NMP, logical nitrogen adds the water that a constant pressure funnel (interior dress molecular sieve) replaces water trap to remove generating in the dereaction before the return line, heated and stirred, be warming up to 60 ℃, reactant dissolves fully, is the brown clear solution, continue to be warming up to 220 ℃, reaction solution is a brown solution, in 200 ℃ of reaction 4h, in the process of cooling solution too thickness can add small amount of methanol dilution, when being cooled to 60 ℃, reaction solution poured in the 150ml methyl alcohol precipitate, filter, washing, dry, get buff powder 5.56g, limiting viscosity is 0.42dL/g, yield 94.3%, Tg is 276 ℃, tensile strength 91Mpa, flexural strength 130Mpa, 261 ℃ of heat-drawn wires.
Embodiment 8
In the 250ml four-hole boiling flask, add 3.24g4 successively, 4 '-two (3-amino-benzene oxygen benzene) sulfone (7.5mmol), 0.62g 4,4 '-diaminodiphenylsulfone(DDS) (2.5mmol), 1.96g pyromellitic acid dianhydride (9mmol), the 20g meta-cresol, 20g NMP, logical nitrogen adds the water that a constant pressure funnel (interior dress molecular sieve) replaces water trap to remove generating in the dereaction before the return line, heated and stirred, be warming up to 60 ℃, reactant dissolves fully, is the brown clear solution, continue to be warming up to 220 ℃, reaction solution is a brown solution, in 180 ℃ of reaction 5h, in the process of cooling solution too thickness can add small amount of methanol dilution, when being cooled to 60 ℃, reaction solution poured in the 150ml methyl alcohol precipitate, filter, washing, dry, get buff powder 5.33g, limiting viscosity is 0.4dL/g, yield 97.6%, Tg is 283 ℃, tensile strength 90Mpa, flexural strength 135Mpa, 268 ℃ of heat-drawn wires.
The comparative example 1:
In the 250ml four-hole boiling flask, add 2.6g diamines 4 successively, 4 '-diaminodiphenylsulfone(DDS) (10mmol), 2.12g pyromellitic acid anhydride (9.7mmol), 0.089g phthalic anhydride (0.6mmol), the 30g meta-cresol, 30g NMP, logical nitrogen, add the water that a constant pressure funnel (interior dress molecular sieve) replaces water trap to remove generating in the dereaction before the return line, heated and stirred is warming up to 60 ℃, reactant dissolves fully, be the brown clear solution, be warming up to 100 ℃, yellow mercury oxide is separated out, continue to be warmed up to 200 ℃, in 200 ℃ of reaction 6h, reaction finishes to be cooled to 60 ℃, reaction soln is poured in the 100ml methyl alcohol precipitated, filter, get buff powder 4.27g, yield 94.9%, limiting viscosity is 0.48dL/g, no second-order transition temperature and fusing point, 238 ℃ of heat-drawn wires.
The comparative example 2
In the 250ml four-hole boiling flask, add 4.32g diamines 4 successively, 4 '-two (3-amino-benzene oxygen benzene) sulfone (10mmol), 2.12g pyromellitic acid anhydride (9.7mmol), 0.089g phthalic anhydride (0.6mmol), the 30g meta-cresol, 30g NMP, logical nitrogen, add the water that a constant pressure funnel (interior dress molecular sieve) replaces water trap to remove generating in the dereaction before the return line, heated and stirred is warming up to 60 ℃, and reactant dissolves fully, be the brown clear solution, continue to be warmed up to 200 ℃, in 200 ℃ of reaction 6h, reaction finishes to be cooled to 60 ℃, faint yellow precipitation is separated out, reaction soln poured in the 100ml methyl alcohol precipitates, filter, buff powder 6.04g, yield 97.9%, limiting viscosity is 0.5dL/g, and Tg is 260 ℃, 241 ℃ of heat-drawn wires.
The resulting polyimide of Comparative Examples, or do not have tangible second-order transition temperature, or have only 260 ℃, heat-drawn wire all is lower than 240 ℃.Product second-order transition temperature of the present invention is all more than 270 ℃, and maximum operation (service) temperature is that heat-drawn wire all is higher than the comparative example more than 20 ℃.
Claims (10)
1. polyimide, the structure that it is characterized in that described polyimide are suc as formula shown in (I), and expression is made up of n unit, and n is a natural number:
Group " A-" in each unit in its Chinese style (I) independently be selected from formula (II) or (III) shown in group:
And have the group shown in formula (II) and the formula (III) in the structure of described polyimide simultaneously, the unit number that contains the group shown in the formula (II) is 1: 0.1～10 with the ratio that contains the unit number of the group shown in the formula (III).
2. polyimide as claimed in claim 1, the limiting viscosity that it is characterized in that described polyimide are at 0.4～0.7dL/g, and second-order transition temperature is more than 270 ℃.
3. polyimide as claimed in claim 1 or 2 is characterized in that the described unit number that contains the group shown in the formula (II) is 1: 1～4 with the ratio that contains the unit number of the group shown in the formula (III).
4. the preparation method of a polyimide as claimed in claim 1, it is characterized in that described preparation method is as follows: organic dianhydride and organic diamine monomer are dissolved in the high boiling solvent, mechanical stirring under protection of inert gas, be heated to 180～220 ℃ of polyreactions 3～7 hours, and again reaction solution poured into precipitation, filtration, washing, drying obtained described polyimide in methyl alcohol, acetone, ethanol or the water; Described organic dianhydride is that structure is suc as formula the pyromellitic dianhydride shown in (IV), described organic diamine be structure shown in formula V 4,4 '-diaminodiphenylsulfone(DDS) and structure are suc as formula 4 shown in (VI), than 1: 0.1～10 mixing, described high boiling solvent is the wherein a kind of of meta-cresol, N-Methyl pyrrolidone, cresols, para-chlorophenol or two or more mixed solvent arbitrarily to 4 '-two (3-amino-benzene oxygen benzene) sulfone with amount of substance;
5. the preparation method of polyimide as claimed in claim 4, the mol ratio that it is characterized in that described organic diamine and organic dianhydride is 0.9～1.1: 1.0.
6. the preparation method of polyimide as claimed in claim 5 is characterized in that described 4,4 '-two (3-amino-benzene oxygen benzene) sulfone and 4, and the amount of substance ratio of 4 '-diaminodiphenylsulfone(DDS) is 1～4: 1.
7. the preparation method of polyimide as claimed in claim 5 is characterized in that the total mass of organic dianhydride and organic diamine accounts for 10～45% of reaction mass total mass.
8. as the preparation method of the described polyimide of one of claim 5～7, it is characterized in that described high boiling solvent is the mixed solvent of meta-cresol and N-Methyl pyrrolidone.
9. the preparation method of polyimide as claimed in claim 8 is characterized in that described high boiling solvent is meta-cresol and N-Methyl pyrrolidone with volume ratio 0.2～5: 1 mixed solvent of forming.
10. as the preparation method of the described polyimide of one of claim 5～7, it is characterized in that described organic dianhydride and organic diamine monomer are dissolved in the high boiling solvent, mechanical stirring under protection of inert gas is heated to 200～205 ℃ of reactions 4～5 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102489A (en) * | 2013-02-27 | 2013-05-15 | 南京岳子化工有限公司 | Thermoplastic polyimide resin and preparation method thereof |
| CN104761898A (en) * | 2014-01-03 | 2015-07-08 | 金东纸业（江苏）股份有限公司 | Water-soluble polyimide resin solution, and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102489A (en) * | 2013-02-27 | 2013-05-15 | 南京岳子化工有限公司 | Thermoplastic polyimide resin and preparation method thereof |
| CN103102489B (en) * | 2013-02-27 | 2015-05-27 | 南京岳子化工有限公司 | Thermoplastic polyimide resin and preparation method thereof |
| CN104761898A (en) * | 2014-01-03 | 2015-07-08 | 金东纸业（江苏）股份有限公司 | Water-soluble polyimide resin solution, and preparation method thereof |
| CN104761898B (en) * | 2014-01-03 | 2017-07-07 | 金东纸业（江苏）股份有限公司 | Water-soluble polyimide resin solution and preparation method thereof |
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Effective date of registration: 20151222 Address after: 224500 Jiangsu Province, Yancheng City Binhai County Binhuai town head Zeng Village (Yancheng City coastal chemical industry park) Patentee after: JIANGSU DINGLONG TECHNOLOGY Co.,Ltd. Patentee after: ZHEJIANG DINGLONG TECHNOLOGY CO.,LTD. Address before: 310016, Qing Chun, building 16, block B, East Qing Chun Road, Jianggan District, Zhejiang, Hangzhou 66, China Patentee before: ZHEJIANG DRAGON CHEMICAL Group Co. |
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Address after: Touluo village, Binhuai Town, Binhai County, Yancheng City, Jiangsu Province Patentee after: JIANGSU DINGLONG TECHNOLOGY Co.,Ltd. Patentee after: Zhejiang DINGLONG Technology Co.,Ltd. Address before: Touluo village, Binhuai Town, Binhai County, Yancheng City, Jiangsu Province Patentee before: JIANGSU DINGLONG TECHNOLOGY Co.,Ltd. Patentee before: ZHEJIANG DINGLONG TECHNOLOGY Co.,Ltd. |
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Effective date of registration: 20230329 Address after: 311228 Linjiang Industrial Park, Xiaoshan District, Zhejiang, Hangzhou Patentee after: Zhejiang DINGLONG Technology Co.,Ltd. Address before: Touluo village, Binhuai Town, Binhai County, Yancheng City, Jiangsu Province Patentee before: JIANGSU DINGLONG TECHNOLOGY Co.,Ltd. Patentee before: Zhejiang DINGLONG Technology Co.,Ltd. |
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